JPH0245474A - Bis (2, 4-organylthio-s-triazine-6-yl) polysulfone, its production and vulcanizable mixture containing the same - Google Patents

Abstract

The invention relates to bis(2,4-organylthio-s-triazin-6-yl) polysulphanes of the general formula (I) <IMAGE> prepared from compounds of the general formula (II) <IMAGE> and an ammonium or alkali metal polysulphide, and to the use of compounds of this type as accelerators in vulcanisable rubber mixtures.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to dinuclear S-
Prior Art Regarding Triazine Compounds, Processes for Their Preparation and Vulcanizable Rubber Mixtures Containing the Same Dinuclear S-triazine compounds having a sulfate chain are described, for example, in West German Patent No. 1,669,954, US Pat. No. 3,923,724 and It is known from the specification No. 4,621,121. In this case, this is bis(2-ethylamino-4-diethylamino-8-triazin-6-yl)disulfane or the corresponding tetrasulfane, which can be used as a vulcanization accelerator in vulcanizable rubber mixtures.

Problem to be Solved by the Invention The object of the invention is a vulcanization accelerator which facilitates the processing of rubber mixtures due to higher scorch times and vulcanization times.

Means for Solving the Problems The object of the present invention has the general formula (I): 0), in which the individual polysulfurs have an integer or fractional value with a statistical average X of 2 to 5, in particular but Bis(2
, 4-organylthio-5-triazin-6-yl) polysulfane.

Other objects of the invention are - ritual (■): [wherein R1, R2 are the same or different, H1 alkyl with 1 to 4 C-atoms of branching or non-merging, C3-
C8 cycloalkyl, especially cyclohexyl, phenyl or 2-7-hydroxyethyl, 3-hydroxypropyl,
Represents 2-hydroxypropyl, (S)x is 2-10
S-triazine derivatives of polysulfane chains (2 x < 1 in which R1 and R2 are as defined above) having S-atoms of the general formula ( [[): Me2Sx [wherein Me is ammonium or alkali cation,
in a molar ratio of from 2:l to 2:1.2 at 0°C.
A process for the preparation of a compound according to claim 1, characterized in that the reaction is carried out at a temperature of from 100 to 100% to the boiling point of the organic solvent and the product is separated and dried.

In general, the starting compound according to formula (I) is initially dissolved in an organic solvent, preferably THF, 1,2-dimethoxyethane or a ketone such as acetone, methyl ethyl ketone and isobutyl methyl ketone, followed by vigorous stirring. a polysulfide corresponding to the formula (I [ It is done like this.

The water proportion of the reaction mixture should not exceed 2-40% by weight.

It is also important for the selection of the organic solvent that the desired product forms as a precipitate, which can then be filtered off without problems, for example.

The S-triazine derivatives used as starting compounds are obtained, for example, from 7 Reims Patent No. 1,592,489.

In a preferred embodiment, the reaction proceeds in the presence of a phase transition catalyst known per se, which corresponds to the formula =(RnNH4-n)"X-
(n −1,2,3~4)(R1)PH4-p:l
"X - (p -3~4) (R'C5H, NR") +X
-(C3H4N is a pyridine ring) and (R11?2R
3S)+X − [In the formula, X is halogen, hydroxide, or hydrogen sulfate (
n5o4-), R is an alkyl group having 1-18 C-atoms, 1-18
represents an alkenyl group, phenyl group, benzyl group having C-atoms of , where the compounds 1 and 2 do not contain more than one of these phenyl- and benzyl groups, R' is hydrogen, 1 to 4 C- R# represents an alkyl- or alkylene group having 1-18 C-atoms; R1, R2 and R3 represent an alkyl- or alkenyl group having 1-18 C-atoms; or phenyl group].

This catalyst is 0 for the 5-1-riazine compound in one ritual ■.
．． It is used in amounts of 1 to 5% by weight.

In their use as vulcanization accelerators, the compounds according to the invention according to the formula (I) are compared to the bis(2-ethylamino-4-diethylamino-3-)riazin-6-yl)tetrasulfane known from the prior art. Depending on the rubber type - higher Muny scorch times, significantly longer vulcanization times, increased crosslinking rates and better reversion behavior are superior.

Another drawback of many conventional accelerators (e.g. most sul-7-amides, thiurams), which should no longer be ignored today, is that during the vulcanization process amines are liberated and, insofar as this is converted into nidroses, the vulcanizate Among other things, it leads to the formation of nidrosamine, which far limits the possibilities of use of this promoter insofar as it is toxic.

The use of the compounds claimed in the invention according to formula (1) includes natural rubber (NR), isoprene rubber (JR), butadiene rubber (BR), styrene-butadiene rubber (S
BR), inbutylene-isoprene rubber (IIR), ethylene-propylene-terpolymer (EPDM), nitrile rubber (NBR), halogen-containing rubber and also epoxidized natural rubber (ENR) and mixtures thereof. Includes rubber mixtures known from the prior art. The use of the compounds according to the claims of the invention is of particular interest in the case of rubber types which give rise to such versions as, for example, natural rubber, isoprene- and butadiene rubber and mixtures thereof with each other or with other rubbers.

During accelerated vulcanization, the bis(24-organylthio-5-tert-riazin-6-yl)polysulfane according to the invention is used as an accelerator in an amount of 0.01-10 parts per 100 parts of rubber.
．． It is especially used in amounts of 0.1 to 5 parts and with a sulfur dosage of 0.1 to 10 parts.

The molar ratio of promoter according to the invention to sulfur (S8) is preferably 1
:0.5 to 1.5.

In order to achieve a specific change in the vulcanization kinetics, 2
or more bis(2,4-organylthio-
It has proven advantageous to use 5-triazin-6-yl) polysulfanes in mixtures, in order to maintain the above-mentioned application rates, in particular favorable promoter/sulfur ratios, in which case the substitution is predominantly molecular. To be implemented.

Similarly, for kinetic reasons, bis(2,4-organylthio-8-triazin-6-yl)polysulfanes are used in mixtures with customary promoters, such as sulfenamides and thiurams. This procedure is sometimes used in pure bis(2,4-organylthio-S-triazine-6
-yl) polysulfane- lead to a burden on reverginone stability compared to vulcanizates.

Nevertheless, conventional accelerators are partially bis(2)
If 14-organylthio-5-)riazin-6-yl)polysulfane is substituted, this also has an adverse effect on the reversion behavior.

Another important influence of the incubation time when using the compounds according to the invention in rubber mixtures is, for example, Santogua
rd@P VI (N -(cyclohexylthio)-
7 talimide), Vulkalent” E (N-
Phenyl-N-()lychloromethylsulfenyl)-penzole sulfinamide and South African Patent No. 8
7/1767 and 87/1768 and in combination with commercially available vulcanization retarders such as those described in US Pat. No. 3,546,185. With increasing addition, the bis(2,4-organylthio-s-triazin-6-yl)polysulfane-containing mixture undergoes a linear increase in the incubation time.

The retarders, in particular those mentioned above and the compounds according to the invention according to the general formula (I), can be used in amounts of 0.1-10,
In particular with a sulfur dosage of 0.5 to 8 parts by weight, 0.5 to 1.5:
1. In particular, a molar ratio of 0.8 to 1.2:l is used.

The use of the compounds according to the invention according to claims 1 to 3 includes, for example, other customary components such as: - customary reinforcing systems, namely furnace black channel black, flame black, thermal black, acetyl black, arc black, CK black; Other and synthetic fillers such as silicic acid, silicate, aluminum oxide hydrate, calcium carbonate and natural fillers such as clay, silicate chalk, chalk, talc etc. and silane modified fillers and mixtures thereof.
Particularly silicic acid and silicates are preferred, and from 5 to 150 parts as sole filler or 10 parts in mixture with soot.
-100 parts (in each case based on 100 parts of rubber) ZnO and stearic acid as accelerators of vulcanization in amounts of 0.5 to 10 parts per 100 parts of rubber - for example I P
Commonly used aging like PD, TMQ-Ozone-1
Waxes and mixtures thereof as fatigue protectants and also as photoprotectants - for example aromatic, naphthenic, paraffinic, synthetic plasticizers and mixtures thereof - optionally for example bis(3-triethoxysilylglopyl)tetrasulfane, 3-chloropropyltriethoxysilane, 3-mercaptoglobiltrimethoxysilane and mixtures thereof in amounts of 0.1 to 20, preferably 1 to 10 parts per 100 parts of filler, optionally sulfur per 100 parts of rubber. Other silanes such as -chloropropyltrialkoxysilanes, vinyltrialkoxysilanes and aminoalkyltrialkoxysilanes and mixtures thereof, such as silicic acid, silicates, clays and others, in amounts of 0.5 to 4 parts. 0.1-1 for every 100 parts of silanol group-containing filler
5. Preferably in amounts of 1 to 10 parts, optionally dyes and processing aids in the customary proportions, in a rubber mixture containing.

Bis(2,4-organylthio-S-triazine-6-
The scope of application of the polysurane is the rubber mixtures according to claims 4 to 7, such as those normally used in tire production, and for example conveyor belts, belts, moldings, rubber tubes with or without fillings, roller rubber coatings. , jackets, injection molded materials, freehand products (Free-ha
ndartikel), seats, soles and uppers, cables, pure rubber tires and their vulcanizates.

The vulcanizable mixtures are produced by generally known methods. For example, an internal mixer with a reflux temperature of about 60° C. is used.

Therein, the sulfur- and promoter-free rubber mixture is premixed and subsequently the promoter and, if appropriate, the sulfur and/or organosilane as adhesion medium are also mixed in in a second step.

EXAMPLE Bis(2,4-methylthio-s-triazin-6-yl)polysulfur 7ane is produced according to the following formula: Example 1 250ffi + 2 multi-headed flasks with stirrer, condenser and thermometer 2.4- Dimethylmercapto-6-chloro-5-triazine (BMT) 5 hmol (=
IO, 3h) Disodium tetrasulfide
3 hmol (-5,239) tetrahytomifuran (THF
) Charge 1 Okff THF at room temperature. Introduce the ground BMT in a mortar while stirring. After complete dissolution, while stirring vigorously (800 Upon), quickly add finely ground Na2Sx (X~4) in a mortar. A white precipitate forms within 5 minutes, and the temperature drops to 30°C.
rises to .

The reaction rate is increased by the addition of 0.3% by weight of a phase transition catalyst, such as benzyltriethylammonium chloride (TEBA). After 60 minutes, the washings are filtered with suction, washed chloride-free with water and dried over P2O5.

Yield: 90% polysuruane (X~4) Melting point: 169~
178°0 Example 2 250+* (2-necked flask, stirrer, condenser, thermometer, dropping funnel (50+*I2)) The amounts used are the same as in Example 1.

Charge THF at room temperature. Introduce the ground BMT in a mortar while stirring.

After completely dissolving Na2Sx (X~4) and water 20
Warm a solution consisting of 0 ml (stirring speed: 8000 ml)
pm). After a few minutes a white precipitate forms and the temperature rises to about 30°C.

Yield: 89% Polysulfane (X~4) Melting point: 160~
180°C Identification of the produced compounds is carried out by: l) Elemental analysis: C5o) (12N 6311CHN
S CL calculated value: 27.26 2.74 19.07 5
0.93 0 measurement value: 27.13 2.75 1
8.80 51.09 0.272) IR-spectrum IR (cm-'): 3435.2929.1
499.1475.1426.1323.1250.1
160.844.783 3) NMR H-NMR (CDCQs, 250MHz):
s, 2.58 ppm" C-NMR (CDC43
, 250MHz) : ppw+ : 13-5(-
Test criteria for the application of S-CHa), 177.187: Physical tests are carried out at room temperature according to the following standard provisions: Version West German Patent No. 2848559 Measurement pa % Scorch Time ASTM 02084
Splitting tear strength DIN 5
3507 N/Tomo Mooney test
DIN 535231524 The following names and abbreviations are used in the minute examples and have the following meanings: Buna 1500: Styrofoam from H1jJs.
Butadiene rubber RSS: Ribbed smoked sheet (natural rubber) C
OI? AX@N 220: Carbon black, surface (BET) 120 points 279 (DEGtlSSA)
Naftolen@ZD: Plasticizer V consisting of hydrocarbons
ulkanox・4010 NA: N-isopropyl-N'phenyl-p-phenylene monodiamine Vulkanox" HS: Poly-2,2,4-trimethyl-1,2-dihydro-quinoline Protector" G 35 Niosin protective wax V 480: Bis( 2-ethylamino-4-diethylamino-S-triazin-6yl) Tetrasulfane V 675 : Bis(2,4-methylthio-3-triazin-6-yl)-polysulfane (X~4) Example 3 In natural rubber Bis(2-ethylamino-4-diethylamino-3-1-
Comparison of rubber industry evaluation with riazin-6-yl)tetrasulfane (V480) RSS l too 1
00CORAX N 200 50
50ZnORS 5
5 Stearic acid 22 Naphtholene ZD 3 3Vul
kanox 4010 NA 2.5
2.5 Volkanox HS 1
5 1.5Protektor G 35
1 1V 480-
3.5V675
3.1 Sulfur 0.31 Vulcanization temperature: 160°C Vulcanization data at 160°C and 795% Vulcanization time (m) 25 tlO% (min) 3.0 4.
2t80%~t20% (min) 3.8 2.4t9
0%~tlO% (min) 12.7 5.2
M5t5 (130℃) (min) 3.6
9.7M5tss (130'o) (min')
6.2 13.1 Tensile strength (MPa)
21.2 21.9 module 300
% (MPa) 10.1 10.4 Tear strength (
N/mm) 21 30 Example 4 N22〇- promoted with bis(2,4-methylthio-3-triazin-6-yl)polysulfane (V675)
Comparison of reversion stability of filled SBR with bis(2-ethylamino-4-diethylamino-5-triazin-6-yl)tetrasulfane (V480) Buna 100 100
CORAX N 220 ZnORS Stearic acid NafLolen ZD Vulkanox 4010 NA Vulkanox HS Protector G 35 Sulfur vulcanization temperature: 170℃ Reversion: 1.8 2.5

Claims (1)

[Claims] 1. General formula I: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are the same or different, H, branched or unbranched 1 to 4 alkyl, allyl, C_3-C_6 cycloalkyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, phenyl, (S)x having from 2 to 10 S-atoms, polysulfane bis(2, 4-organylthio-S-triazine-6
−il) polysulfan. 2. General formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 are the same or different, and have H, branched or unbranched 1 to 4 C-atoms alkyl, allyl, C_3-C_6 cycloalkyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, phenyl, (S)x is a polysulfane chain with 2 to 10 S-atoms (2≦x≦ bis(2,4-organylthio-S- triazine-6
-il) In the production method of polysulfane, S of the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 represent the above]
- a triazine compound of the general formula III: Me_2Sx, in which Me represents an ammonium- or alkali cation and Sx corresponds to the above, in an organic solvent or a mixture thereof with water from 0°C to A process for the preparation of bis(2,4-organylthio-S-triazin-6-yl)polysulfane, characterized in that the reaction is carried out at temperatures up to the boiling point and the product is subsequently separated. 3. The reaction is expressed by the following formula: [RnNH_4_-_n]^+X^- (in the formula, n=1, 2
, 3-4) [RpPH_4_-_p]^+X^- (in the formula p = 3-4) [R'C_5H_4NR'']^+X^-(
In the formula, C_5H_4N is a pyridine ring) and [R_1R_2R_3S]^+X^- [X = halogen or hydroxide, hydrogen sulfate (HSO_4^-), R = alkyl group having 1 to 18 C-atoms, 1 to 18
alkenyl radicals, phenyl radicals, benzyl radicals having C-atoms of , where compounds 1 and 2 have no more than one of these phenyl- and benzyl radicals, R'=hydrogen, having from 1 to 4 C-atoms; alkyl- or alkylene radicals, R″=alkyl- or alkenyl radicals with 1 to 18 C-atoms, R^1, R^2 and R^3 = alkyl- or alkenyl radicals with 1-18 C-atoms; or phenyl group]
3. The process as claimed in claim 2, wherein the process proceeds in the presence of a phase transition catalyst corresponding to . 4. In vulcanizable mixtures based on one or more natural and/or synthetic rubbers, containing fillers, sulfur and other commonly used ingredients, the general formula I: ▲Mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are the same or different, H, branched or fused alkyl having 1 to 4 C-atoms, allyl, C_3 to C_6 cycloalkyl, 2-hydroxyethyl, 3-Hydroxypropyl, 2-hydroxypropyl, phenyl, (S) 0.01 to 10 parts of at least one compound represented by Vulcanizable mixture, characterized in that it contains a proportion of sulfur of 1.5 parts, in each case based on 100 parts of rubber. 5. A vulcanizable mixture according to claim 4, containing a retarder and at least one compound according to formula I in a molar ratio of 0.5 to 1.5:1. 6. Claim 4 or 5, containing only silicic acid as a filler.
Vulcanizable mixture as described. 7.Silicic acid 10~ at the same time as carbon black as a filler
6. A vulcanizable mixture according to claim 4, comprising 100 parts based on 100 parts of rubber.